U.S. patent number 11,369,557 [Application Number 16/494,750] was granted by the patent office on 2022-06-28 for concentrate comprising at least one mannosylerythritol lipid and at least one polyglycerol and fatty acid ester.
This patent grant is currently assigned to OLEON NV. The grantee listed for this patent is OLEON NV. Invention is credited to Hilde Peeters.
United States Patent |
11,369,557 |
Peeters |
June 28, 2022 |
Concentrate comprising at least one mannosylerythritol lipid and at
least one polyglycerol and fatty acid ester
Abstract
The invention relates to a concentrate comprising at least one
mannosylerythritol lipid and at least one polyglycerol and fatty
acid ester, to a method for the production thereof, and to the uses
of same, particularly as a thickening, foaming and/or cleaning
agent.
Inventors: |
Peeters; Hilde (Keerbergen,
BE) |
Applicant: |
Name |
City |
State |
Country |
Type |
OLEON NV |
Evergem |
N/A |
BE |
|
|
Assignee: |
OLEON NV (Evergem,
BE)
|
Family
ID: |
1000006399918 |
Appl.
No.: |
16/494,750 |
Filed: |
March 16, 2018 |
PCT
Filed: |
March 16, 2018 |
PCT No.: |
PCT/EP2018/056710 |
371(c)(1),(2),(4) Date: |
September 16, 2019 |
PCT
Pub. No.: |
WO2018/167285 |
PCT
Pub. Date: |
September 20, 2018 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20200093725 A1 |
Mar 26, 2020 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A61K
8/60 (20130101); A61Q 1/14 (20130101); A61K
8/042 (20130101); A61K 8/375 (20130101); A61K
2800/48 (20130101) |
Current International
Class: |
A61K
8/60 (20060101); A61Q 1/14 (20060101); A61K
8/37 (20060101); A61K 8/04 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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|
|
0579159 |
|
Jan 1998 |
|
EP |
|
2468842 |
|
Dec 2016 |
|
EP |
|
3115355 |
|
Jan 2017 |
|
EP |
|
2011168548 |
|
Sep 2011 |
|
JP |
|
WO-2017158194 |
|
Sep 2017 |
|
WO |
|
Other References
Schott. Comments on Hydrophile-Lipophile Balance Systems. J. Pharm.
Sciences, 1990, 79(1):86-88. (Year: 1990). cited by examiner .
International Search Report received in PCT/EP2018/056710 dated May
7, 2018 with English Translation. cited by applicant .
Mintel, "Vino Moisturizing Face Mask", http://www.gnpd.com, Mar.
2014. cited by applicant .
Fukuoka et al., "Enzymatic Synthesis of a Novel Glycolipid
Biosurfactant, Mannosylerythritol Lipid-D and its Aqueous Phase
Behavior," Carbohydrate Research, vol. 346, 2011, pp. 266-271.
cited by applicant .
Rau et al., "Downstream Processing of Mannosylerythritol Lipids
Produced by Pseudoyma Aphidis," Eur. J. Lipid Sci. Technol., vol.
107, 2005, pp. 373-380. cited by applicant.
|
Primary Examiner: Wax; Robert A
Assistant Examiner: Tcherkasskaya; Olga V.
Attorney, Agent or Firm: Arentfox Schiff LLP
Claims
The invention claimed is:
1. A concentrate comprising: 20% to 70% by weight of at least one
mannosylerythritol lipid (MEL), with respect to the total weight of
the concentrate, and at least one polyglycerol fatty acid ester
selected from the group consisting of polyglycerol-6 isostearate,
polyglycerol-10 isostearate, polyglycerol-10 diisostearate,
polyglycerol-6 laurate, polyglycerol-6 myristate, polyglycerol-6
stearate, polyglycerol-6 oleate, polyglycerol-10 oleate,
polyglycerol-10 caprylate, polyglycerol-6 caprylate, polyglycerol-4
caprate, polyglycerol-4 laurate, polyglycerol-10 laurate, and
combinations thereof, wherein a weight ratio mannosylerythritol
lipid(s)/polyglycerol fatty acid ester(s) ranges from 1/3 to 2/1,
and wherein a foam formed from an aqueous solution comprising said
concentrate does not change its volume by more than 10% in 10
minutes from formation of the foam.
2. The concentrate according to claim 1, wherein the the weight
ratio mannosylerythritol lipid(s)/polyglycerol fatty acid ester(s)
ranges from 1/2 to 2/1.
3. The concentrate according to claim 1, comprising at least two
MELs selected from the group consisting of MELs-A, MELs-B, MELs-C
and MELs-D.
4. The concentrate according to claim 1, further comprising at
least one glycerol fatty acid ester.
5. The concentrate according to claim 4, wherein the at least one
glycerol fatty acid ester is a glycerol caprylic acid ester.
6. A composition comprising: at least one MEL, at least one
polyglycerol fatty acid ester selected from the group consisting of
polyglycerol-6 isostearate, polyglycerol-10 isostearate,
polyglycerol-10 diisostearate, polyglycerol-6 laurate,
polyglycerol-6 myristate, polyglycerol-6 stearate, polyglycerol-6
oleate, polyglycerol-10 oleate, polyglycerol-10 caprylate,
polyglycerol-6 caprylate, polyglycerol-4 caprate, polyglycerol-4
laurate, polyglycerol-10 laurate, and combinations thereof, and
water, wherein a weight ratio mannosylerythritol
lipid(s)/polyglycerol fatty acid ester(s) is from 1/3 to 2/1, and
wherein a total quantity of MEL(s) and polyglycerol fatty acid
ester(s) is from 3% and 75% by weight of the total weight of the
composition.
7. A composition in a form of a solution, comprising: at least one
MEL, at least one polyglycerol fatty acid ester selected from the
group consisting of polyglycerol-6 isostearate, polyglycerol-10
isostearate, polyglycerol-10 diisostearate, polyglycerol-6 laurate,
polyglycerol-6 myristate, polyglycerol-6 stearate, polyglycerol-6
oleate, polyglycerol-10 oleate, polyglycerol-10 caprylate,
polyglycerol-6 caprylate, polyglycerol-4 caprate, polyglycerol-4
laurate, polyglycerol-10 laurate, and combinations thereof, and
water, wherein a weight ratio mannosylerythritol
lipid(s)/polyglycerol fatty acid ester(s) is from 1/3 to 2/1, and
wherein a total quantity of MEL(s) and polyglycerol fatty acid
ester(s) expressed as a percentage by weight of the total weight of
the composition is from 0.05 to less than 3.
8. A thickening agent, foaming agent and/or cleaning agent
comprising the concentrate according to claim 1.
9. A method for cleaning a hard surface, dish, or human comprising
applying to the hard surface, dish, or human the composition
according to claim 6 with water.
10. A method for partially or totally replacing a surfactant in a
shampoo or dishwashing detergent, comprising partially or totally
replacing the surfactant with the concentrate according to claim 1,
wherein the surfactant is selected from the group consisting of
sodium lauryl sulphate, sodium lauryl ether sulphate, cocamide
diethanolamine, and combinations thereof.
11. A shampoo or dishwashing detergent comprising the concentrate
of claim 1.
12. A method of thickening water comprising adding the concentrate
of claim 1 to water.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a National Stage Entry of PCT/EP2018/056710,
filed Mar. 16, 2018, which claims priority to French Patent
Application No. 1752241 filed on Mar. 17, 2017, the disclosure of
which are hereby incorporated by reference in its entirety.
The present invention relates to a concentrate and to compositions
comprising same. The present invention also relates to a process
for the preparation of the concentrate and of the compositions
according to the invention and uses thereof, in particular use of
the concentrate according to the invention as a thickening, foaming
and/or cleaning (detergent) agent.
Thickening, foaming and/or cleaning agents are used in many fields.
It is known in particular to use thickening, foaming and/or
cleaning agents in cosmetics, for example in makeup removal
compositions. It is also known to use thickening, foaming and/or
cleaning agents in the cleaning industry, for example in the
preparation of cleaning or detergent products such as household or
industrial maintenance compositions, in particular compositions for
cleaning hard surfaces, or dishwashing products.
Cocamide diethanolamine (or cocamide DEA) is a surfactant having
good foaming and thickening properties, usually used in cleaning
compositions such as dishwashing products, or in cosmetics. It is
also common to use sulphated compounds, such as sodium lauryl
sulphate (SLS) or sodium lauryl ether sulphate (SLES). These
sulphated surfactants have very good foaming and cleaning
properties. Cocamide DEA and the sulphated compounds can be used in
combination, so as to combine the foaming, thickening and cleaning
properties of these compounds.
However, cocamide DEA and the sulphated compounds such as SLS and
SLES are regarded as substances that are hazardous to human
health.
In particular, cocamide DEA is thought to be a potential
carcinogen.
As regards SLS and SLES, they are irritants to the skin and eyes.
Furthermore, these compounds are corrosive, and would thus cause
the deterioration of the lipids and fats of which the muscles and
skin are composed. Moreover, SLS and SLES are generally
contaminated with a carcinogen, 1,4-dioxane, which is a by-product
of the manufacturing process of these sulphated compounds.
Therefore there is currently a need for solutions to replace these
hazardous substances.
More particularly, it would be beneficial to develop agents: having
a good surface-active property, having at the same time good
thickening, foaming and/or cleaning properties, allowing stable
foams to be obtained, and that would be less toxic to users.
The work of the inventor has made it possible to demonstrate that a
specific concentrate had all of the above-described advantageous
properties.
The invention thus relates to a concentrate comprising: at least
20% by weight of at least one mannosylerythritol lipid, with
respect to the total weight of the concentrate, and at least 30% by
weight of at least one polyglycerol fatty acid ester, with respect
to the total weight of the concentrate, in which the ratio of
mannosylerythritol lipid(s)/polyglycerol fatty acid ester(s) is
comprised within the range [1/3; 3/1].
It will be noted that within the framework of the present
application, unless otherwise stated, by "ratio" is meant the ratio
by weight and the ranges of values indicated are understood
inclusive of boundaries.
By "mannosylerythritol lipid" or MEL is meant a surfactant
comprising a hydrophilic part formed by the mannosylerythritol
group, and a hydrophobic part formed by at least one acyl
group.
By MEL is meant more particularly a molecule having the following
general formula (I):
##STR00001##
in which: R.sup.1 and R.sup.2, identical or different, represent an
acyl group, comprising an unsaturated or saturated, acyclic
carbon-containing chain, R.sup.3 and R.sup.4, identical or
different, represent an acetyl group or a hydrogen atom, and
R.sup.5 represents a hydrogen atom or an acyl group.
Among the MELs of formula (I) described above, the "di-acylated
MELs" and "tri-acylated MELs" can be distinguished according to the
nature of the group present in position R.sup.5. It will be noted
that according to this terminology, the acetyl groups capable of
being present in positions R.sup.3 and R.sup.4 are not accounted
for in the acyl groups.
By "tri-acylated MEL" is meant a molecule of formula (I) in which:
R.sup.1 and R.sup.2, identical or different, represent an acyl
group, comprising an unsaturated or saturated, acyclic
carbon-containing chain, R.sup.3 and R.sup.4, identical or
different, represent an acetyl group or a hydrogen atom, and
R.sup.5 represents an acyl group.
By "di-acylated MEL" is meant a molecule of formula (I) in which:
R.sup.1 and R.sup.2, identical or different, represent an acyl
group, comprising an unsaturated or saturated, acyclic
carbon-containing chain, R.sup.3 and R.sup.4, identical or
different, represent an acetyl group or a hydrogen atom, and
R.sup.5 represents a hydrogen atom.
A di-acylated MEL is thus represented by the following formula
(II):
##STR00002##
Advantageously, the at least one MEL comprised in the concentrate
according to the invention is di-acylated.
Two stereoisomers of di-acylated MEL of formula (II) are known and
represented in formulae (III) and (IV) below:
##STR00003## in which R.sup.1, R.sup.2, R.sup.3, R.sup.4 are
identical to those indicated in formula (II).
Advantageously, a di-acylated MEL is a molecule of formula
(III).
Formulae (I) to (IV) above can represent several molecules, each
molecule therefore being a MEL. By "MELs" is meant at least two
molecules of formulae (I), (II), (III) or (IV) different by virtue
of their substitution (acyl, acetyl groups), or by virtue of their
stereoisomerism, more particularly, at least two different
molecules of formulae (III).
Furthermore, the MELs are generally classified in four classes of
molecules, denoted A to D, according to their degree of acetylation
in positions R.sup.3 and R.sup.4. The class of the MELs-A comprises
molecules of formula (I) having two acetyl groups in positions
R.sup.3 and R.sup.4. The class of the MELs-B and the class of the
MELs-C comprise molecules of formula (I) having a single acetyl
group in positions R.sup.4 and R.sup.3 respectively. Finally, the
class of the MELs-D comprises molecules of formula (I) having no
acetyl group (R.sup.3=R.sup.4.dbd.H).
As well as by their degree of acetylation, the MELs can vary in
their structure, by the nature of the fatty acids of which their
hydrophobic part is composed. This variation is generally a
function of the process utilized for obtaining the MELs.
The MELs are generally obtained by processes utilizing the
cultivation of fungi, and more particularly of yeasts.
Advantageously, the MEL(s) to which the present application relates
are obtained by a fermentation process, comprising the following
steps: cultivation of a fungi strain and more particularly of a
yeast strain in the presence of a carbon source in order to obtain
MELs, and recovery of the MELs thus obtained.
The strains from which it is possible to obtain MELs are well known
to a person skilled in the art. By way of example, it is known to
use strains of the family of the Basidiomycetes, preferably of the
genus Pseudozyma, such as Pseudozyma antarctica, Pseudozyma
parantarctica, Pseudozyma aphidis, Pseudozyma rugulosa, Pseudozyma
graminicola, Pseudozyma siamensis, Pseudozyma hubeiensis,
Pseudozyma tsukubaensis, Pseudozyma crassa, or of the genus
Ustilago, such as Ustilago maydis, Ustilago cynodontis and Ustilago
scitaminea.
In general, depending on the strain, a class of MELs (MELs-A,
MELs-B, MELs-C or MELs-D) is mainly or even exclusively produced
with respect to the other classes of MEL. By way of example,
Pseudozyma antarctica, Pseudozyma aphidis, Pseudozyma rugulosa and
Pseudozyma parantarctica produce mainly MELs-A of formula (III).
Pseudozyma graminicola, Pseudozyma siamensis, Pseudozyma hubeiensis
produce mainly MELs-C of formula (III). Pseudozyma tsukubaensis
produces mainly MELs-B of formula (IV) and Pseudozyma crassa
produces mainly MELs-A of formula (IV).
Advantageously, the MELs are obtained by a fermentation process
utilizing a strain producing MELs of formula (III).
More particularly, the MELs are obtained by a fermentation process
utilizing a strain selected from Pseudozyma aphidis, Pseudozyma
rugulosa Pseudozyma antarctica or Pseudozyma parantarctica,
preferentially from Pseudozyma aphidis, Pseudozyma antarctica or
Pseudozyma parantarctica, more preferentially, the strain is
Pseudozyma aphidis.
The carbon-containing substrate is typically a glycerol, an
n-alkane or an oil, in particular of renewable origin.
Any oil, composed of triglycerides and liquid at the temperature of
the fermentation process, can be used as carbon-containing
substrate.
Preferentially, the renewable oil is a vegetable or animal oil,
more preferentially, a vegetable oil. In particular, the vegetable
oil is selected from the group constituted by a soya oil, a
sunflower oil, an olive oil and a rapeseed oil. More particularly,
the vegetable oil is a soya oil or a rapeseed oil, even more
particularly, a rapeseed oil.
These renewable oils are particularly rich in acyl groups
comprising a carbon-containing chain with 18 carbon atoms, such as
the acyl groups originating from oleic, linoleic and/or linolenic
acid.
The fermentation process generally lasts at least 3 days,
preferentially at least 7 days.
According to a preferential embodiment, the MELs are obtained by a
fermentation process utilizing: a strain of the genus Pseudozyma,
preferentially Pseudozyma antarctica, Pseudozyma parantarctica, or
Pseudozyma aphidis, a vegetable oil, preferentially a rapeseed oil
or a soya oil, as carbon-containing substrate.
Such a strain is usually cultured in a reactor in a medium
comprising glucose, water and/or salts (such as magnesium sulphate,
monopotassium phosphate, sodium nitrate and/or ammonium nitrate).
This culture medium is also utilized in the fermentation process.
In fact, in general, the fermentation medium of the fermentation
process comprises a culture medium and the carbon-containing
substrate.
Advantageously, the different components of the medium (glucose and
strain in particular) are sterilized separately before introduction
into the reactor.
The temperature of the medium is preferably comprised between
20.degree. C. and 40.degree. C., more preferentially between
25.degree. C. and 35.degree. C.
The crude reaction medium obtained at the end of the fermentation
process is what is called the crude fermentation medium in the
present application.
The crude fermentation medium generally comprises at least two
di-acylated MELs, at least residual carbon-containing substrate
and/or a by-product of the carbon-containing substrate, the strain
and water, the by-product of the carbon-containing substrate
resulting from the fermentation.
The step of recovering the MELs is intended to separate one or more
MEL(s) from one or more of the other components of the crude
fermentation medium, such as residual carbon-containing substrate
and/or a by-product of the carbon-containing substrate, a strain
and/or water.
According to the preferential embodiment above, the crude
fermentation medium comprises at least two di-acylated MELs, at
least one triglyceride and/or at least one fatty acid, water and a
strain of the genus Pseudozyma.
In fact, when the carbon-containing substrate is an oil of
renewable origin, a by-product of the carbon-containing substrate
is a fatty acid. In addition, as a vegetable oil is mainly (more
than 90% by weight) constituted by triglycerides, the residual
vegetable oil is thus composed of at least one triglyceride.
The separation of one or more MEL(s) from one or more of the other
components of the crude fermentation medium can be carried out by
any separation method known to a person skilled in the art.
Advantageously, the separation of one or more MEL(s) from one or
more of the other components can comprise one or more of the
following methods: settling, centrifugation, filtration,
evaporation, liquid/liquid extraction, passing over a mineral
substrate or a resin.
In particular: the strain can be separated by settling, filtration,
and/or centrifugation; the water can be separated by settling,
evaporation, centrifugation, and/or passing over a mineral
substrate which is an adsorbent; the fatty acids and the
triglycerides can be separated by liquid/liquid extraction and/or
by passing over a mineral substrate or a resin.
The recovered MELs can thus comprise: at least one triglyceride
and/or at least one fatty acid, and optionally, a strain.
By "fatty acid" is meant a fatty acid that is free and/or in the
form of a salt.
The quantity of fatty acid(s) and/or of triglyceride(s) present in
the recovered MELs can be comprised between 0.5 and 60% by weight,
preferably between 1 and 50% by weight, with respect to the total
weight of recovered MELs.
Advantageously, the fatty acid(s) comprise(s) a carbon-containing
chain comprising between 8 and 24 carbon atoms, preferably between
8 and 20 carbon atoms.
Advantageously, the triglyceride(s) comprise(s) acyl groups the
saturated or unsaturated, acyclic carbon-containing chain of which
comprises between 8 and 24 carbon atoms, preferably between 16 and
18 carbon atoms. More particularly, the carbon-containing chain is
linear and comprises only carbon and hydrogen atoms, optionally
substituted by a hydroxyl (OH) function.
The recovered MELs can therefore be in a more or less purified
form, i.e. in a mixture with other components of the fermentation
medium.
More particularly, in the present application, and in particular in
the examples, when the recovered MELs are in a mixture with at
least one fatty acid and/or at least one triglyceride, optionally
water and/or a strain, this mixture is called "mixture of
MELs".
A first mixture of MELs is a crude fermentation medium, i.e. at
least two di-acylated MELs with the other components of the crude
fermentation medium.
The crude fermentation medium can be subjected to one or more
separation methods, leading to other preferred mixtures of MELs
having the following features: a content of MELs greater than or
equal to 30% by weight, preferentially greater than or equal to 40%
by weight, more preferentially greater than or equal to 50% by
weight; a content of other components (including fatty acid(s),
triglyceride(s), water and/or strain) less than or equal to 70% by
weight, preferentially less than or equal to 60% by weight, more
preferentially less than or equal to 50% by weight; the percentages
by weight being given with respect to the weight of the mixture of
MELs.
More particularly, depending on the separation method(s) such as
those described above, mixtures of MELs with a greater or lesser
concentration of MELs can be obtained.
According to a first embodiment, the mixture of MELs has the
following features: a content of MELs greater than or equal to 55%
by weight; a content of other components (including fatty acid(s),
triglyceride(s), water and/or strain) less than or equal to 45% by
weight; the percentages by weight being given with respect to the
weight of the mixture of MELs.
Advantageously, in this first embodiment, the water and/or strain
content is less than or equal to 10% by weight, preferentially less
than or equal to 5% by weight, with respect to the weight of the
mixture of MELs.
According to a second embodiment, which is particularly preferred,
the mixture of MELs has the following features: a content of MELs
greater than or equal to 90% by weight, preferentially greater than
or equal to 95% by weight, more preferentially greater than or
equal to 98% by weight; a content of other components (including
fatty acid(s), triglyceride(s), water and/or strain) less than or
equal to 10% by weight, preferentially less than or equal to 5% by
weight, more preferentially less than or equal to 2% by weight; the
percentages by weight being given with respect to the weight of the
mixture of MELs.
Advantageously, in this second embodiment, the water and/or strain
content is less than or equal to 2% by weight, with respect to the
weight of the mixture of MELs.
Such a mixture of MELs can for example be obtained using a
fermentation process such as described above, comprising several
separation steps such as described above, these separation steps
preferentially including a liquid/liquid extraction and/or passing
over a mineral substrate.
Passing over a mineral substrate can be a chromatography, such as
an adsorption chromatography on a silica column, carried out using
suitable solvents. Such solvents are known to a person skilled in
the art.
Examples of mixtures of MELs and of a process for the production
thereof are also described in the following publication:
"Downstream processing of mannosylerythritol lipids produced by
Pseudozyma aphidis"; Rau et al.; European Journal of Lipids Science
and Technology (2005), 107, 373-380.
Advantageously, the MEL(s) recovered at the end of the fermentation
process described above is/are di-acylated.
When the MEL(s) recovered at the end of the fermentation process
is/are one or more di-acylated MEL(s), it is possible to utilize a
subsequent step of production of tri-acylated MELs starting from
the one or more recovered di-acylated MEL(s) (or from a mixture of
di-acylated MELs).
This subsequent step advantageously comprises: dissolution of the
one or more di-acylated MEL(s) in an organic solvent in the
presence of an enzyme; and addition of at least one vegetable oil,
at least one fatty acid of vegetable origin or at least one fatty
acid ester of vegetable origin; under conditions allowing either a
transesterification reaction between the di-acylated MEL(s) and the
triglycerides present in the vegetable oil or the fatty acid ester
of vegetable origin, or an esterification reaction between the
di-acylated MEL(s) and the fatty acid of vegetable origin, thus
allowing the production of tri-acylated MEL(s).
Advantageously, the organic solvent is selected from methanol,
ethanol, propanol, butanol, acetone, propanone, butanone,
pentan-2-one, 1,2-ethanediol, 2,3-butanediol, dioxane,
acetonitrile, 2-methyl-butan-2-ol, tert-butanol, 2-methylpropanol,
4-hydroxy-2-methyl pentanone, tetrahydrofuran, hexane,
dimethylformamide (DMF), dimethylsulphoxide (DMSO) and/or
pyridine.
Preferentially, the vegetable oil is selected from the group
constituted by a soya oil, a sunflower oil, an olive oil and a
rapeseed oil. More particularly, the vegetable oil is a soya oil or
a rapeseed oil, even more particularly, a rapeseed oil.
Advantageously, the fatty acid of vegetable origin or the fatty
acid ester of vegetable origin originates from a soya oil, a
sunflower oil, an olive oil or a rapeseed oil. More particularly,
the fatty acid of vegetable origin or the fatty acid ester of
vegetable origin originates from a soya oil or a rapeseed oil, even
more particularly, from a rapeseed oil.
These vegetable oils are particularly rich in acyl groups
comprising a carbon-containing chain with 18 carbon atoms, such as
in the acyl groups originating from oleic, linoleic and/or
linolenic acid.
The enzyme can be selected from lipases, proteases and/or
esterases, preferably from lipases and/or esterases, even more
preferentially from lipases.
Advantageously, the esterification or transesterification reaction
is carried out during approximately 12 to 72 hours at a temperature
close (+/-10.degree. C.) to the optimal temperature of activity of
the enzyme, preferably during approximately 24 to 48 hours at a
temperature comprised between 20 and 30.degree. C., more
preferentially at 25.degree. C.
The tri-acylated MEL(s) can then be recovered from the reaction
medium, by separation methods known to a person skilled in the
art.
For example chromatography, such as adsorption chromatography on a
silica column, is included among these separation methods.
The concentrate according to the invention also comprises at least
30% by weight of at least one polyglycerol fatty acid ester, with
respect to the total weight of the concentrate.
Preferably, the concentrate according to the invention comprises a
polyglycerol fatty acid ester.
Advantageously, the fatty acid comprised in the polyglycerol fatty
acid ester comprises a carbon-containing chain comprising between 6
and 18 atoms.
As the polyglycerol fatty acid ester is intended to be solubilized
in water, it is hydrophilic, advantageously with an HLB greater
than or equal to 9, preferentially greater than or equal to 10,
more preferentially greater than or equal to 12.
By HLB (Hydrophilic-Lipophilic Balance) is meant the balance
between the dimension and the force of the hydrophilic group and
the dimension and the force of the lipophilic group of the
surfactant. The HLB value according to GRIFFIN is defined in J.
Soc. Cosm. Chem. 1954 (Volume 5), pages 249-256.
By way of example of polyglycerol fatty acid esters having an HLB
greater than or equal to 9, there may be mentioned polyglycerol-6
isostearate, polyglycerol-10 isostearate, polyglycerol-10
diisostearate, polyglycerol-6 laurate, polyglycerol-6 myristate,
polyglycerol-6 stearate, polyglycerol-6 oleate, polyglycerol-10
oleate, polyglycerol-10 caprylate, polyglycerol-6 caprylate,
polyglycerol-4 caprate, polyglycerol-4 laurate, polyglycerol-10
laurate.
Preferably, the polyglycerol comprised in the polyglycerol fatty
acid ester comprises between 2 and 12, preferably between 2 and 10,
more preferentially between 3 and 6 units of glycerol.
Advantageously, the polyglycerol of the polyglycerol fatty acid
ester is a polyglycerol-4, polyglycerol-6 or polyglycerol-10. The
integer following the polyglycerol (or PG) represents the number of
glycerol units forming the polyglycerol.
Preferentially, the polyglycerol fatty acid ester is a polyglycerol
fatty acid monoester or a polyglycerol fatty acid diester, more
preferentially a polyglycerol fatty acid monoester.
The concentrate according to the invention has a good thickening
property. By "thickening property" is meant that the concentrate
according to the invention increases the viscosity of water. In
other words, a composition comprising a concentrate according to
the invention and water will have a viscosity greater than that of
water alone, advantageously of at least 30 mPas, preferably of at
least 80 mPas, more preferentially of at least 200 mPas, even more
preferentially of at least 300 mPas.
Moreover, the concentrate according to the invention makes it
possible to give water the appearance of a gel, i.e. that a
composition comprising a concentrate according to the invention and
water will present the appearance of a gel.
By "gel appearance" is meant the typical rheology of a gel. In
particular, the initial viscosity of a composition comprising a
concentrate according to the invention and water will decrease if
it is subjected to friction, and will return to its initial value
once the friction has ceased.
These features of the concentrate according to the invention are
described in greater detail in Example 2 below.
Furthermore, the concentrate according to the invention has a good
foaming property. It is understood here that, when placed in
contact with water, a concentrate according to the invention allows
the formation of a foam on the surface of the composition
obtained.
Preferably, the concentrate according to the invention allows the
formation of a foam under conditions similar to those described in
standard ASTM D892.
In the present application, any reference to a standard is a
reference to the standard current at the date of filing.
Advantageously, the volume of the foam formed on the surface of a
composition comprising a concentrate according to the invention and
water is greater than 200 mL, preferably greater than 400 mL, even
more preferentially greater than 600 mL. Such a volume varies as a
function of the hardness of the water.
Furthermore, the foam formed on the surface of a composition
comprising a concentrate according to the invention is stable. By
"stable" is meant that the volume of foam formed does not decrease
or decreases very little over time, i.e. by less than 50 mL in 10
min, preferentially less than 25 mL in 10 min.
The foaming property of the concentrate according to the invention
as well as the stability of a foam formed on the surface of a
composition comprising the concentrate according to the invention
are described in greater detail in Example 3.
Moreover, the concentrate according to the invention has a good
cleaning property. Advantageously, the concentrate according to the
invention comprises at least 30% by weight, optionally at least 45%
by weight of at least one MEL, with respect to the total weight of
the concentrate.
Advantageously, at least 80% by weight of the concentrate according
to the invention is constituted by mannosylerythritol lipid(s) and
polyglycerol fatty acid ester(s).
Preferably, in the concentrate according to the invention, the
ratio by weight of mannosylerythritol lipid(s) and polyglycerol
fatty acid ester(s) is comprised within the range [1/2; 2/1].
Such a ratio makes it possible to further improve the thickening
property of the concentrate according to the invention.
Preferably, the at least one polyglycerol fatty acid ester
comprised in the concentrate according to the invention is a
polyglycerol capric and/or caprylic acid ester.
A polyglycerol capric and/or caprylic acid ester is also called
polyglycerol caprate and/or caprylate, or polyglyceryl caprate
and/or caprylate.
Preferably, the at least one ester is a polyglycerol capric acid
ester.
Alternatively, the at least one polyglycerol fatty acid ester is a
polyglycerol fatty acid ester comprising 18 carbon atoms,
preferably a polyglycerol oleic or isostearic acid ester.
Advantageously, the concentrate according to the invention
comprises at least two MELs, in particular at least two MELs
originating from different classes, selected from the group
constituted by the MELs-A, MELs-B, MELs-C and MELs-D.
According to a first advantageous embodiment, the concentrate
according to the invention comprises MELs-A, MELs-B, MELs-C and
optionally MELs-D, more preferentially MELs-A, MELs-B, MELs-C and
MELs-D.
Advantageously, the concentrate according to the invention
comprises MELs-A and MELs-B at a content comprised between 50% and
95% by weight, preferably 60% to 85% by weight, the percentages by
weight being indicated with respect to the weight of the total
quantity of MELs.
Advantageously, the concentrate according to the invention
comprises MEL(s)-C at a content greater than or equal to 5% by
weight, preferentially greater than 10% by weight, the percentages
by weight being indicated with respect to the weight of the total
quantity of MELs.
More particularly, the concentrate according to the invention
comprises MELs-A and MELs-B at a content comprised between 60% and
80% by weight and MELs-C at a content greater than or equal to 15%
by weight, the percentages by weight being indicated with respect
to the weight of the total quantity of MELs.
According to a second advantageous embodiment, the concentrate
according to the invention comprises MELs-D at a content comprised
between 75% and 100% by weight, preferably between 90% and 100% by
weight, the percentages by weight being indicated with respect to
the weight of the total quantity of MELs.
The MELs-D can be obtained by deacetylation of the MELs-A, MELs-B
and MELs-C. An example of a deacetylation reaction of the MELs-A,
MELs-B and MELs-C using a hydrolyzing enzyme is described in the
following publication: "Enzymatic synthesis of a novel glycolipid
biosurfactant, mannosylerythritol lipid-D and its aqueous phase
behavior"; Fukuoka et al.; Carbohydrate Research (2011), 346,
266-271.
Advantageously, the concentrate according to the invention also
comprises at least one glycerol fatty acid ester.
Preferably, the concentrate according to the invention comprises a
glycerol fatty acid ester.
According to a first embodiment of the concentrate according to the
invention, the latter comprises or consists of: at least 20% by
weight of at least one mannosylerythritol lipid, with respect to
the total weight of the concentrate, and at least 30% by weight of
at least one polyglycerol fatty acid ester, with respect to the
total weight of the concentrate, in which the ratio by weight of
mannosylerythritol lipid(s)/polyglycerol fatty acid ester(s) is
comprised within the range [1/3; 3/1].
According to a second embodiment of the concentrate according to
the invention, the latter comprises or consists of: at least 20% by
weight of at least one mannosylerythritol lipid, with respect to
the total weight of the concentrate, at least 30% by weight of at
least one polyglycerol fatty acid ester, with respect to the total
weight of the concentrate, and at least one glycerol fatty acid
ester, in which the ratio by weight of mannosylerythritol
lipid(s)/polyglycerol fatty acid ester(s) is comprised within the
range [1/3; 3/1].
The at least one polyglycerol fatty acid ester utilized in these
two embodiments is advantageously a polyglycerol capric and/or
caprylic acid ester, preferably a polyglycerol capric acid
ester.
Advantageously, in the concentrate according to the invention, the
quantity of glycerol fatty acid ester(s) is comprised between 1.5%
and 4.5% by weight, preferably between 2 and 4% by weight of the
total weight of the concentrate.
The above-described preferred features of the concentrate according
to the invention are applicable to these embodiments as a
whole.
Preferably, the at least one glycerol fatty acid ester comprised in
the concentrate according to the invention is a glycerol caprylic
acid ester.
When added to water, the glycerol caprylic acid ester causes a
bloom effect in water. This effect is very beneficial for
developing cosmetic products, such as those for which it is desired
to obtain a milky texture.
A composition, such as a cosmetic composition, prepared from a
concentrate according to the invention comprising glycerol caprylic
acid ester will have advantageous properties, such as a pleasant
feel without an oily film, and gives the user a sensation of skin
nourishment.
Glycerol caprylic acid esters also have good antimicrobial
properties.
The invention also relates to a process for the preparation of a
concentrate according to the invention, comprising a step of mixing
at least 20% by weight of at least one mannosylerythritol lipid,
with respect to the total weight of the concentrate, and at least
30% by weight of at least one polyglycerol fatty acid ester, with
respect to the total weight of the concentrate, in which the ratio
by weight of mannosylerythritol lipid(s)/polyglycerol fatty acid
ester(s) is comprised within the range [1/3; 3/1].
Advantageously, the mixture is produced at a temperature comprised
between 40 and 60.degree. C., preferably 60.degree. C.
Advantageously, the components utilized in the process for the
preparation of a concentrate according to the invention have one or
more of the above-described preferred features.
The invention further relates to a composition comprising a
concentrate according to the invention, and water. More
particularly, the composition according to the invention comprises:
at least one MEL, at least one polyglycerol fatty acid ester having
an HLB greater than or equal to 9, and water, in which the ratio by
weight of mannosylerythritol lipid(s)/polyglycerol fatty acid
ester(s) having an HLB greater than or equal to 9 is comprised
within the range [1/3; 3/1].
The at least one MEL and the at least one polyglycerol fatty acid
ester are such as described above, including the advantageous and
preferential modes.
The composition according to the invention has a good cleaning, and
more particularly makeup removal, property. This is described in
greater detail in Example 6 below.
According to a first embodiment, the quantity of concentrate or the
total quantity of MEL(s) and polyglycerol fatty acid ester(s)
having an HLB greater than or equal to 9 in the composition
according to the invention is comprised between 3% and 75% by
weight of the total weight of the composition.
By total quantity of MEL(s) and polyglycerol fatty acid ester(s)
having an HLB greater than or equal to 9 is meant the total
quantity by weight of molecules of MEL(s) and molecules of
polyglycerol fatty acid ester(s).
According to this first embodiment of the composition according to
the invention, the latter has a viscosity much greater than that of
water, and has the appearance of a gel.
According to a particular mode of this first embodiment, the
composition according to the invention comprises a concentrate
according to the invention that has no glycerol fatty acid ester.
In this particular mode, when the quantity of concentrate or the
total quantity of MEL(s) and polyglycerol fatty acid ester(s)
having an HLB greater than or equal to 9 comprised in the
composition according to the invention is small, i.e. comprised
between 3% and 7% by weight of the total weight of the composition,
it is preferable for the concentrate or the total quantity of
MEL(s) and polyglycerol fatty acid ester(s) having an HLB greater
than or equal to 9 to comprise at least 50% by weight of at least
one MEL, with respect to the total weight of concentrate or of the
total quantity of MEL(s) and polyglycerol fatty acid ester(s)
having an HLB greater than or equal to 9, respectively. Such a MEL
content makes it possible to obtain a notable increase in the
viscosity of water.
According to a particular alternative mode of this first
embodiment, the composition according to the invention comprises at
least one glycerol fatty acid ester. In this particular mode, a
notable increase in the viscosity of water is obtained even at a
content of at least 20% by weight of MEL(s) with respect to the
total weight of concentrate or of the total quantity of MEL(s) and
polyglycerol fatty acid ester(s) having an HLB greater than or
equal to 9.
According to this first embodiment, the quantity of concentrate or
the total quantity of MEL(s) and polyglycerol fatty acid ester(s)
having an HLB greater than or equal to 9 in the composition
according to the invention is advantageously comprised between 5
and 50% by weight, preferably between 5 and 35% by weight, of the
total weight of the composition.
Increasing concentrate contents make it possible to increase the
viscosity of the composition according to the invention. A person
skilled in the art is capable of defining or adapting the quantity
of concentrate in the composition making it possible to obtain a
desired viscosity.
According to this embodiment, the composition according to the
invention advantageously has a dynamic viscosity greater than or
equal to 40 mPas, preferably greater than or equal to 200 mPas,
more preferentially greater than or equal to 400 mPas, even more
preferentially greater than or equal to 500 mPas.
According to a second embodiment, the quantity of concentrate in
the composition according to the invention, expressed as a
percentage by weight of the total weight of the composition, is
comprised within the range [0.05; 3)
According to this second embodiment of the composition according to
the invention, the latter has a viscosity that is not much greater
than that of water, and is presented in the form of a solution.
According to this second embodiment, the quantity of concentrate is
advantageously comprised between 0.1 and 2% by weight, preferably
between 0.15 and 1.5% by weight, with respect to the total weight
of the composition.
The invention also relates to a process for the preparation of a
composition according to the invention, comprising a step of mixing
a concentrate according to the invention with water.
According to a first embodiment of the process for the preparation
of a composition according to the invention, the at least one MEL
is mixed with at least one polyglycerol fatty acid ester having an
HLB greater than or equal to 9, before mixing with water.
According to a second embodiment of the process for the preparation
of a composition according to the invention, the at least one MEL
is mixed with water independently of a polyglycerol fatty acid
ester.
Advantageously, the mixing step is carried out under stirring.
The invention also relates to the use of a concentrate according to
the invention as a thickening, foaming and/or cleaning agent.
The concentrate according to the invention can be used in any type
of application in which it is usual to use a thickening, foaming
and/or cleaning agent.
This concentrate can be used as a thickening, foaming and/or
cleaning agent in the preparation of cleaning or detergent products
such as household or industrial maintenance compositions, in
particular compositions for cleaning hard surfaces, or dishwashing
products.
This concentrate can also be used in cleaning products in the
petroleum industry.
Finally, this concentrate can be used as a thickening, foaming
and/or cleaning agent in cosmetics or hygiene products.
The invention also relates to the use of a composition according to
the invention as a cleaning composition.
The composition according to the invention can be used in any type
of application in which it is usual to use cleaning
compositions.
By way of example, the composition according to the invention can
be used as a cleaning or detergent composition, for example as a
household or industrial maintenance composition, in particular as a
composition for cleaning hard surfaces, or as a dishwashing
product.
The composition according to the invention can also be used in the
petroleum industry.
Advantageously, the composition according to the invention is used
as a hygiene product or in cosmetics, preferably as a washing
and/or makeup removal composition.
This composition can be used in order to form a lather with water,
or can be applied directly to the skin without adding water.
In particular, the composition according to the invention in the
first embodiment thereof, as described above, has the appearance of
a gel, and will therefore advantageously be used to form a lather
with water.
For example, the user may apply water to the part of the body to be
cleaned, then apply the composition according to the invention to
this part, and finally rub in order to lather said composition.
The composition according to the invention in the first embodiment
thereof may also be used as a base for a hygiene product such as a
micellar gel.
The composition according to the invention in the second embodiment
thereof, as described above, is in the form of a solution, and thus
will advantageously be applied directly to the skin, such as the
skin of the face, for example using a cotton pad.
By "solution" is meant a liquid having a dynamic viscosity at
25.degree. C. less than 40 mPas.
The invention also relates to the use of a concentrate according to
the invention, partially or totally replacing a surfactant selected
from the group constituted by sodium lauryl sulphate, sodium lauryl
ether sulphate and/or cocamide diethanolamine.
The invention will be better understood in the light of the
following examples, given by way of illustration, with reference to
the following figures:
FIG. 1, which is a diagram representing the stability over time of
foams formed on the surface of compositions prepared from
concentrates according to the invention and starting from sulphated
compounds or from MELs;
FIG. 2, which comprises 2 photographs, a and b, illustrating the
cleaning property of a composition according to the invention and
of comparative compositions.
EXAMPLE 1: PREPARATION OF CONCENTRATES ACCORDING TO THE
INVENTION
1. Obtaining MELs
The MELs were obtained by a fermentation process comprising the
following steps: culturing a yeast strain such as Pseudozyma
aphidis in the presence of a vegetable oil (rapeseed) in order to
obtain the MELs; and recovering the MELs thus obtained.
At the end of the step of recovering the MELs, a first mixture of
MELs (mixture of MELs 1A) is obtained, which has the following
features: Content of MELs: 55% by weight Content of other
components: 45% by weight (including 42% by weight of free fatty
acids and triglycerides and 3% by weight of water and strain), the
percentages by weight being given with respect to the total weight
of the mixture of MELs obtained.
A step of purification of the mixture of MELs 1A was then carried
out by adsorption chromatography on a silica column, with the use
of a mixture of solvents having an increasing polarity gradient. A
second mixture of MELs (mixture of MELs 1B) was thus obtained,
which has the following features: Content of MELs: at least 98% by
weight with respect to the total weight of the mixture of MELs
obtained.
In particular, each of the mixtures of MELs 1A and 1B comprises
MELs-A at a content of 52% by weight, MELs-B at a content of 12% by
weight, MELs-C at a content of 35% by weight, and MELs-D at a
content of 1% by weight, the percentages by weight being given with
respect to the weight of the total quantity of MELs.
2. Polyglycerol Fatty Acid Esters
Radia.RTM. 7932 from OLEON was used. This product is composed of
polyglycerol-4 capric acid esters (polyglycerol-4 caprate or
polyglyceryl-4 caprate). The purity thereof in polyglycerol fatty
acid esters is greater than 95%.
Polyglycerol-10 oleic, capric and isostearic acid esters were
prepared according to the esterification process with a fatty acid
(oleic acid, Radiacid 0215 from OLEON, capric acid, Radiacid 610
from OLEON and isostearic acid, Radiacid 0909 from OLEON) and
polyglycerol-10 from SPIGA NORD, in a 1/1 molar ratio. The fatty
acid and polyglycerol are mixed in the presence of calcium
hydroxide and heated at 220.degree. C. until the acid number is
less than 1 mgKOH/g.
3. Glycerol Fatty Acid Ester
Radia.RTM. 7907 from OLEON was used. This product is composed of
glycerol caprylic acid esters (glycerol monocaprylate or glyceryl
monocaprylate).
4. Preparation of Concentrates According to the Invention
The compounds are mixed manually in a suitable vessel, according to
the formulations indicated in Table 1 hereinafter at a temperature
of 60.degree. C., until homogenization of the concentrate.
Preferably, the temperature should not exceed 60.degree. C.
The different concentrates prepared are summarized in the following
Table 1:
TABLE-US-00001 TABLE 1 Concentrates according to the invention
prepared in Example 1 Mixture of Radia .RTM. Radia .RTM. MELs 1B
7932 7907 PG-10 PG-10 PG-10 (%) (%) (%) Oleate caprylate
isostearate Concentrate 1 25 75 -- Concentrate 2 33.3 66.7 --
Concentrate 3 50 50 -- Concentrate 4 66.7 33.3 Concentrate 5 25
70.8 4.2 Concentrate 6 33.3 62.9 3.8 Concentrate 7 50 47.2 2.8
Concentrate 8 66.7 31.44 1.86 Concentrate 15 50 2.8 47.2
Concentrate 16 50 2.8 47.2 Concentrate 17 50 2.8 47.2 *The
percentages indicated are percentages by weight with respect to the
total weight of concentrate.
EXAMPLE 2: EVALUATION OF THE THICKENING PROPERTY OF THE
CONCENTRATES ACCORDING TO THE INVENTION AND OF COMPARATIVE
CONCENTRATES
The thickening property of the concentrates according to the
invention and of comparative concentrates was evaluated.
1. Equipment and Methods
1.1. Equipment
The following products were used: concentrates 1 to 8 prepared in
Example 1 the mixture of MELs 1B prepared in Example 1 Radia.RTM.
7932 (OLEON) Radia.RTM. 7907 (OLEON) demineralized water
The following equipment was used: glass flasks a spatula a
rheometer (TA Instruments AR 2000).
1.2. Methods
Concentrates According to the Invention
Concentrates 1 to 8 prepared in Example 1 were used.
Preparation of the Comparative Concentrates
The different compounds are mixed manually in a suitable vessel, at
a temperature of 60.degree. C., until the concentrate is
homogenized. When MELs are used in the preparation of the
concentrate, the temperature preferably should not exceed
60.degree. C.
The different comparative concentrates prepared are summarized in
the following Table 2.
TABLE-US-00002 TABLE 2 Comparative concentrates prepared in Example
2 Mixture of MELs Radia .RTM. 7907 1B (%) Radia .RTM. 7932 (%) (%)
Comparative 0 100 -- concentrate 9 Comparative 10 90 -- concentrate
10 Comparative 100 0 -- concentrate 11 Comparative 0 94.4 5.6
concentrate 12 Comparative 10 84.96 5.04 concentrate 13 Comparative
15 80.24 4.76 concentrate 14 *The percentages indicated are
percentages by weight with respect to the total weight of
concentrate.
Evaluation of the Thickening Property of Concentrates 1 to 14
10% by weight of concentrates 1 to 8 according to the invention and
comparative concentrates 9 to 14 were respectively added to 90% by
weight of water in glass flasks, the % by weight being indicated
with respect to the total weight of each composition obtained. The
addition of water in the flasks containing the different
concentrates is carried out under manual stirring with a
spatula.
The dynamic viscosity of compositions 1 to 14 was evaluated, using
a rheometer, at a temperature of 25.degree. C. and at a speed of 10
rpm.
The dynamic viscosity of the water (control) is 1 mPA.s.
The appearance of the different compositions was also evaluated by
the naked eye.
The results are presented in Table 3 hereinafter.
TABLE-US-00003 TABLE 3 Dynamic viscosity and appearance of
compositions 1 to 14 prepared in Example 2 Viscosity (mPa s)
Appearance Composition 1 Concentrate 1 44 Partial gel according to
the according to the appearance, one invention invention + water
phase Composition 2 Concentrate 2 48 Partial gel according to the
according to the appearance, one invention invention + water phase
Composition 3 Concentrate 3 586 Gel appearance, according to the
according to the one phase invention invention + water Composition
4 Concentrate 4 980 Gel appearance, according to the according to
the one phase invention invention + water Composition 5 Concentrate
5 56 Gel appearance, according to the according to the one phase
invention invention + water Composition 6 Concentrate 6 400 Gel
appearance, according to the according to the one phase invention
invention + water Composition 7 Concentrate 7 500 Gel appearance,
according to the according to the one phase invention invention +
water Composition 8 Concentrate 8 70 Gel appearance, according to
the according to the one phase invention invention + water
Comparative Comparative 5 Clear water composition 9 concentrate 9 +
appearance water Comparative Comparative 13 Two phases composition
10 concentrate 10 + water Comparative Comparative 5 Two phases
composition 11 concentrate 11 + water Comparative Comparative 5.5
Clear water composition 12 concentrate 12 + appearance water
Comparative Comparative 4.5 1 phase, cloudy, composition 13
concentrate 13 + translucent water Comparative Comparative >5 1
phase, cloudy, composition 14 concentrate 14 + translucent
water
The results show that compositions 1 to 8 comprising a concentrate
according to the invention and water have a dynamic viscosity
greater than that of pure water, and also have the appearance of a
gel. On the other hand, compositions 9 to 14 comprising comparative
concentrates have a viscosity close to that of water and do not
have the appearance of a gel.
A concentrate according to the invention makes it possible to
increase the viscosity of water. It is understood here that a
composition comprising a concentrate according to the invention and
water will have a viscosity greater than that of water alone.
The concentrate according to the invention thus has a good
thickening property, and therefore can be used as a thickening
agent.
Moreover, a concentrate according to the invention makes it
possible to give water the appearance of a gel.
EXAMPLE 3: EFFECT OF THE QUANTITY OF CONCENTRATE ON THE VISCOSITY
OF WATER
Compositions comprising different quantities of concentrate 2
according to the invention prepared in Example 1 and water were
prepared according to the method described in Example 2.
Viscosity measurements were carried out, in the same way as in
Example 2.
The results are shown in Table 4 hereinafter.
TABLE-US-00004 TABLE 4 Effect of the quantity of concentrate on the
viscosity of water Quantity of concentrate (%) Quantity of water
(%) Viscosity (mPa s) 1 99 7 3 97 9 5 95 18 10 90 48 15 85 141 20
80 175 30 70 981 50 50 4380 *The percentages indicated are
percentages by weight with respect to the total weight of the
composition.
The results show that increasing quantities of concentrates
according to the invention make it possible to increase the
viscosity of water.
EXAMPLE 4: EVALUATION OF THE FOAMING PROPERTY OF A CONCENTRATE
ACCORDING TO THE INVENTION AND OF COMPARATIVE
CONCENTRATES--EVALUATION OF THE STABILITY OF THE FOAMS OBTAINED
1. Equipment and Methods
1.1. Equipment
The following products were used: concentrate 7 according to the
invention prepared in Example 1 concentrates 15 and 16 prepared in
Example 1 comparative concentrate 11 prepared in Example 2 SLES
water.
The following equipment was used: water bath, flow meter, a device
for streaming air at 94 mL/min.
1.2. Methods
The protocol implemented is based on that described in standard
ASTM D892.
0.02%, 0.2% and 2% by weight of the concentrate 7 and respectively
99.98%, 99.8% and 98% by weight of water were added to test tubes,
in order to obtain 3 compositions to be tested. Respectively 2% by
weight of concentrates 15 and 16 were introduced into another two
tubes, as well as 98% by weight of water.
The test tubes were then placed in a temperature-controlled bath.
After 15 minutes, the desired temperature of 25.degree. C. was
reached.
Air was then pumped through a porous spherical stone diffuser in
each composition to be tested. Thus small air bubbles are created,
which form a dispersion of air in water. A foam is formed if the
gas bubbles rise to the surface and are not broken beforehand. The
gas-filled bubbles have walls of fine liquid lamellae. The
compositions to be tested are maintained at a temperature of
25.degree. C., and are subjected to air pumping for 5 minutes. The
airflow is then stopped.
The volume of foam formed on the surface of each of the
compositions obtained from concentrate 7, from concentrate 15 and
from concentrate 16 was evaluated, directly after stopping the
airflow.
The time necessary for the foam to break up is observed for the
compositions comprising 0.2% and 2% by weight of concentrate 7, as
well as for the compositions comprising respectively 2% by weight
of concentrate 15 and 2% by weight of concentrate 16. More
particularly, the stability of the foam on the surface of this
composition was evaluated by measuring the volume of foam as a
function of time. More specifically, the volume of foam was
evaluated during 10 minutes after formation thereof, at time
intervals of 60 seconds.
Throughout the entire time necessary for the measurements, the
compositions to be tested are maintained at a temperature of
25.degree. C.
An identical test was carried out for compositions to be tested
comprising 0.2% by weight of comparative concentrate 11 (MELs),
0.2% and 0.5% by weight of sodium lauryl ether sulphate (SLES) and
respectively 99.8%, 99.8% and 99.5% by weight of water, with
respect to the total weight of the composition. SLES is used as a
reference. SLES is a surfactant having very good foaming and
detergent (cleaning) properties.
2. Results
Foaming Property
The results are presented in Table 5 hereinafter.
TABLE-US-00005 TABLE 5 Foaming property of concentrates 7, 15 and
16 according to the invention and of comparative concentrate 11 and
of SLES Quantity of Quantity of water Volume of foam Concentrate
concentrate (%) (%) formed (mL) 7 0.02 99.98 210 0.2 99.8 500 2 98
700 15 2 98 760 16 2 98 700 11 0.2 99.8 600 SLES 0.2 99.8 500 SLES
0.5 99.5 700
These results show that the volumes of foam formed on the surface
of the compositions comprising concentrates 7, 15 or 16 according
to the invention are large.
A concentrate according to the invention thus has a very good
foaming property. It is understood here that when a concentrate
according to the invention is placed in contact with water, it
allows the formation of a large volume of foam on the surface of
the composition obtained.
Moreover, the composition to be tested comprising 0.2% by weight of
concentrate 7 according to the invention made it possible to obtain
a foam having a volume similar to a foam obtained with a
composition comprising 0.2% by weight of sodium lauryl ether
sulphate and 99.8% by weight of water, with respect to the total
weight of the composition.
A concentrate according to the invention is a good replacement
solution for sodium lauryl ether sulphate, or for sodium lauryl
sulphate.
Stability of the Foams
The results are presented in FIG. 1.
These results show that the foams obtained with concentrates 7, 15
and 16 according to the invention were stable during the 10 minutes
of the test, i.e. the volume of these foams did not decrease or
decreased very little in 10 minutes.
The foams obtained with SLES, in particular that obtained from the
composition comprising 0.2% by weight of SLES, were less stable
during the 10 minutes of the test, a reduction in the volume of
these foams being visible in FIG. 1.
Thus, the foam formed on the surface of a composition comprising a
concentrate according to the invention is stable. By "stable" is
meant that the volume of foam formed does not decrease or decreases
very little over time, i.e. by less than 50 mL in 10 min,
preferentially less than 25 mL in 10 min.
Although the composition comprising 0.2% by weight of comparative
concentrate 11 forms a large volume of foam, this volume is not
stable and drops rapidly (-100 mL in 1 minute, -350 mL in 10
minutes), as can be seen in FIG. 1.
EXAMPLE 5: EVALUATION OF THE SURFACE-ACTIVE PROPERTY OF
CONCENTRATES ACCORDING TO THE INVENTION AND OF COMPARATIVE
CONCENTRATES
1. Equipment and Methods
1.1. Equipment Concentrates 3 and 7 according to the invention
prepared in Example 1 Pure water KRUSS K100 tensiometer
1.2. Methods
Surface Tensions
Concentrates 3 and 7 according to the invention were added at
different concentrations to pure water and measurements of surface
tensions were taken.
The surface tension was measured using the tensiometer, using the
Wilhelmy plate method.
The surface tension of the pure water was also measured. It is 71.4
mN/m.
The results are shown in Table 6 hereinafter.
TABLE-US-00006 TABLE 6 Surface tensions Quantity of concentrate in
Concentrate water (%) Surface tension (mN/m) 3 0.02 27.6 3 0.2 27.6
3 2 27.3 *The percentages indicated are percentages by weight with
respect to the total weight of the composition.
The results presented in Table 6 show in particular that a
concentrate according to the invention makes it possible to reduce
the surface tension of water. A concentrate according to the
invention can thus for example be used in cleaning
applications.
Interfacial Tensions
Concentrates 3 and 7 according to the invention, followed by
mineral oil, were added at different concentrations to pure water,
and measurements of interfacial tensions were taken.
The interfacial tension of a water/mineral oil preparation was also
measured. It is approximately 43 mN/m.
The results are shown in Table 7 hereinafter.
TABLE-US-00007 TABLE 7 Interfacial tensions Quantity of concentrate
in water Interfacial tension Concentrate (%) (mN/m) 3 0.02 1.1 3
0.2 0.6 3 2 0.2 7 0.02 1.1 7 0.2 0.6 7 2 0.2 *The percentages
indicated are percentages by weight with respect to the total
weight of the composition.
The values for interfacial tensions obtained with the concentrates
according to the invention are sufficiently low for a concentrate
according to the invention to have the capacity to disperse a
mineral oil in water. A concentrate according to the invention can
thus for example be used in cleaning applications.
EXAMPLE 6: CLEANING PROPERTY OF A COMPOSITION ACCORDING TO THE
INVENTION--APPLICATION IN COSMETICS
1. Equipment and Methods
1.1. Equipment
The following products were used: composition 7 according to the
invention prepared in Example 2 composition 3 according to the
invention prepared in Example 2 sodium lauryl sulphate (VWR.RTM.,
100% pure) water.
The following equipment was used: glass jars with lids, white caps
of 15-mL bottles makeup (foundation, True Match.TM., Super
Blendable Makeup, L'OREAL.RTM.).
1.2. Methods
Water and the composition to be tested were added to a glass
jar.
A white cap is then covered with makeup, then immersed in the glass
jar. The glass jar is closed with its lid and then subjected to
stirring at 244 rpm for 60 minutes.
At the end of 60 minutes, the proportion of makeup that was removed
from the cap and transferred to the mixture of water/composition to
be tested is measured.
The percentage of makeup removed is calculated according to the
following formula: 100-(weight of makeup on the cap before the
experiment-weight of makeup on the cap after the
experiment).times.100/weight of makeup on the cap before the
experiment.
In Experiment 1 below, this method was utilized in order to
evaluate the makeup removal property of composition 7 according to
the invention prepared in Example 2 and of comparative
compositions. The comparative compositions comprise SLS. Like SLES,
SLS is a surfactant having very good foaming and detergent
(cleaning) properties.
In Experiment 2 below, this method was utilized in order to
evaluate the makeup removal property of composition 3 according to
the invention prepared in Example 2.
Experiment 1
The detail of the tests carried out and the results are presented
in Table 8 hereinafter.
TABLE-US-00008 TABLE 8 Tests and results of Experiment 1 % of
makeup Test Composition to be tested removed Test 1 1 g of
composition 7 according to the invention 95.92 in 49 g of water
Test 2 5 g of composition 7 according to the invention 99.07 in 49
g of water Comparative 0.05 g of sodium lauryl sulphate in 50 g of
90.70 test 3 water Comparative 0.25 g of sodium lauryl sulphate in
50 g of 98.37 test 4 water Test 5 Water alone 71.72 (control)
The results of Experiment 1 are also presented in FIG. 2
(comprising photographs a and b).
It can be seen in the photograph that the proportion of makeup that
was removed from the cap and transferred to the mixture of
water/composition 7 according to the invention (glass jars marked 1
and 2) is greater than that removed from the caps and transferred
into the water/comparative composition mixtures (glass jars marked
3 and 4) and into water alone (glass jar marked 5).
This is also apparent from photograph b, which shows the quantity
of makeup that was removed from the caps at the end of each test 1
to 5.
The cap numbered 0 in photograph b corresponds to a control cap
before insertion in a glass jar.
These results show that composition 7 according to the invention
has a makeup removal property equivalent to, or even greater than,
that of the comparative compositions based on sodium lauryl
sulphate.
Experiment 2
The detail of the tests carried out and the results are presented
in Table 9 hereinafter.
TABLE-US-00009 TABLE 9 Tests and results of Experiment 2 % of
makeup Test Composition to be tested removed Test 6 1 g of
composition 3 according to the invention in 90.99 49 g of water
Test 7 5 g of composition 3 according to the invention in 97.69 49
g of water Test 8 Water alone 70.76 (control)
It can be seen that the proportion of makeup that was removed from
the cap and transferred to the mixture of water/composition 3
according to the invention (tests 6 and 7) is appreciably greater
than that removed from the caps and transferred into water alone
(test 8).
EXAMPLE 7: REPLACING COCAMIDE DIETHANOLAMINE (COCAMIDE DEA) AND/OR
SODIUM LAURYL ETHER SULPHATE (SLES) BY A CONCENTRATE ACCORDING TO
THE INVENTION
Concentrate 7 according to the invention was used in the
preparation of cleaning compositions of the detergent type for
dishwashing or shampoo, by replacing cocamide DEA and/or SLES.
Cocamide DEA is a surfactant having good foaming and thickening
properties.
The viscosity of the prepared compositions after one day was
evaluated according to the method described in Example 2.
The volume of foam formed on the surface of the different
compositions was evaluated according to the method described in
Example 4.
The detail of the prepared cleaning compositions and the results of
the different measurements are indicated in Table 10 hereinafter.
The cleaning compositions are prepared by simple mixing of the
components thereof.
TABLE-US-00010 TABLE 10 Prepared compositions and results of tests
9 to 16 of Example 7 Test 9 Test 10 Test 11 Test 12 Test 13 Test 14
Test 15 Test 16 %* Euramid V 3 (cocamide DEA) SLES (28% active) 45
45 40 30 20 10 5 0 Concentrate 7 0 3 8 18 28 38 43 48 according to
the invention Sodium benzoate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 NaCl
0 or 2 0 or 2 0 or 2 0 or 2 0 or 2 0 or 2 0 or 2 0 or 2 Water qsf
100 qsf 100 qsf 100 qsf 100 qsf 100 qsf 100 qsf 100 qsf 100 pH 5-6
5-6 5-6 5-6 5-6 5-6 5-6 Viscosity after 1 40 10 120 6100 7500 24500
29000 25000 days (without NaCl) Viscosity after 1 6300 2020 1320
4100 8600 15200 17700 20900 days (with NaCl) Appearance clear clear
clear Foam, Foam, Foam, Foam, Foam, cloudy cloudy clear cloudy
cloudy Foam after 1 850 760 780 770 800 900 780 850 minute (with
NaCl) Foam after 10 860 760 780 770 800 880 760 830 minutes (with
NaCl) *The percentages indicated are percentages by weight with
respect to the total weight of the composition.
The results show that replacing SLES with increasing quantities of
the concentrate according to the invention results in an increase
in viscosity. This increase in viscosity is obtained despite the
absence of cocamide DEA and NaCl.
Furthermore, the volume of foams formed on the surface of the
different compositions is large.
A concentrate according to the invention is therefore a good
solution for replacing cocamide DEA, sodium lauryl ether sulphate
and/or sodium lauryl sulphate.
More particularly, a detergent composition prepared from a
concentrate according to the invention will have both a high
viscosity and a good foaming property.
Concentrates 15 and 17 according to the invention were also used in
the preparation of cleaning compositions of the detergent type for
dishwashing or shampoo, by replacing cocamide DEA and/or SLES
(tests 17 and 18 respectively).
The pH of these compositions was adjusted to 5.8 by adding citric
acid.
The viscosity of the prepared compositions after one day was
evaluated according to the method described in Example 2.
The volume of foam formed on the surface of the different
compositions was evaluated according to the method described in
Example 4.
The detail of the cleaning compositions prepared and the results of
the different measurements are indicated in Table 11 hereinafter.
The cleaning compositions are prepared by simple mixing of the
components thereof.
TABLE-US-00011 TABLE 11 Prepared compositions and results of tests
17 and 18 of Example 7 Test 17 Test 18 %* Euramid V 3 3 (cocamide
DEA) SLES (28% active) 20 20 Concentrate 15 28 according to the
invention Concentrate 17 28 according to the invention Sodium
benzoate 0.5 0.5 NaCl 0 0 Water qsf 100 qsf 100 pH 5.8 5.8
Viscosity after 1 7230 9032 day (without NaCl) Appearance cloudy
cloudy Foam after 10 770 820 minutes *The percentages indicated are
percentages by weight with respect to the total weight of the
composition.
Again, the results show that the concentrates according to the
invention are a good solution for replacing SLES.
In comparison with test 13 using concentrate 7, tests 17 and 18
show that concentrates 15 and 17 also allow an increase in
viscosity, in particular in the absence of NaCl.
Furthermore, the volume of the foams formed on the surface of the
different compositions is large.
A cleaning composition, such as a shampoo, prepared from a
concentrate according to the invention will have both a high
viscosity and a good foaming property.
* * * * *
References